Method for preparing emulsifying agents and emulsions prepared therefrom



United States Patent METHOD FOR PREPARING EMULSIFYING AGENTS ANDEMULSIONS PREPARED THEREFROM Clyde Lee Aldridge, Baker, and ElphegeMaxime Charlet, Baton Rouge, La., assiguors to Esso Research andEngineering Company, a corporation of Delaware No Drawing. ApplicationJune 13, 1955 Serial No. 515,233

20 Claims. (Cl. 106285) This invention relates to a method for preparingemul' sions of hydrocarbon polymers and more particularly relates to thepreparation of an emulsifying agent from the hydrocarbon polymer to beemulsified and subsequently using this agent for the emulsification.

It is known to prepare emulsions of hydrocarbon polymers by dissolvingthe polymer in a suitable solvent, emulsifying the solution with waterin the presence of a suitable emulsifier and stripping off the solvent.However, it is very difiicult to prepare an emulsion which is stableafter the stripping step. This is a very vigorous step and emulsionsotherwise stable often break when an attempt is made to strip off thesolvent.

It is therefore the main object of this invention to provide a methodfor the emulsification of high molecular weight hydrocarbon polymerswhich will either avoid the solvent stripping step or produce such astable emulsion that the difiiculties usually inherent are no longerpresent.

It is a further object of this invention to provide a novel emulsifyingagent that will produce an emulsion of hydrocarbon polymers with waterwhich will possess unusual mechanical and chemical stability.

It is a still further object of this invention to prepare emulsifyingagents and surfactants from the hydrocarbon polymer to be emulsified.

It is another object of the invention to prepare emulsions fromhydrocarbon polymers by treating the hydrocarbon to convert a portionthereof to an emulsion which acts to emulsify the remaining polymer. f

According to one embodiment of the invention these objects areaccomplished by reacting any hydrocarbon I applicable include thecopolymer'of 97% isobutylene and 3% isoprene prepared by low temperatureFriedel-Crafts polymerization and known as Butyl rubber; the copolymerof 1090% isobutyleneand 90100% styrene also prepared by low temperatureFriedel-Craft polymerization;

resins prepared-by the low temperature Friedel-Craftspolymerization ofsteam-cracked petroleum fractions;

liquid andsolidpolymers of butadiene and copolymers of,

ice

and 24 hours depending on the temperature employed. A catalyst such astertiary butyl hydroperoxide or ditertiary butyl peroxide may be used,if desired. The preparation of these adducts from the liquid copolymersof to preferably 80%, butadiene andv 15 to 25%, preferably 20%, styreneis described in U. S. Patent 2,652,342, issued September 15, 1953, inthe name of Anthony H. Gleason, while the preparation of the adduct fromresins obtained by the low temperature Friedel- Crafts polymerization ofsteam-cracked petroleum feed stocks is described in copendingapplication Ser. No. 448,357, filed August 6, 1954, in the names of JohnF. McKay and Joseph F. Nelson. Reference is hereby made to each of thesefor further details which are incorporated herein by reference. Theanhydride adducts of the other polymers are prepared in a similarmanner.

In accordance with the present invention these anhydride adducts areconverted to salts by reacting them with a basic compound of an alkalimetal or ammonium such as the hydroxides or carbonates of sodium,potassium, lithium, rubidium, calcium or ammonium or with organic basessuch as amines or 'tetrasubstituted ammonium hydroxides. This isaccomplished simply by dissolving the polymer-anhydride adduct in asuitable solvent and mixing it with an aqueous solution of the basiccompound. The salt forms as a jelly-like material which separates fromthe water. In this form it is a potent emulsifier for the polymer fromwhich it was formed or for any other of the hydrocarbon polymers namedabove as well as for saturated type polymers, such as polyisobutylene.

It is not necessary, however, to isolate the alkali metal or nitrogenbase salt of the polymer. It is only necessary to add a small amount(0.1 to 5%) of the anhydride adduct to a solution of a polymer andthen'emulsify by adding water containing enough alkali to neutralize theanhydride groups and agitating. Similarly a large amount of anunsaturated polymer may be emulsified by reacting it with a small amount(.01 to .5%) of the anhydride followed by agitation with an aqueoussolution of an alkali such as the hydroxide or carbonate of the alkalimetals and ammonium or tetra-substituted ammonium hydroxides or organic"bases. The emulsions formed by organic bases and ammonium compoundsdifier from those formed from alkali metal bases in that they can bebroken at will simply by heating to drive off the ammonia.

In forming the emulsion it is preferred to use distilled water ornatural soft water but most waters suitable for human consumption can beused. Hard waters may require preliminary chemical treatment toprecipitate the polyvalent minerals thereof in the form of stablecompounds which will remain inert to the emulsion ingredients if theprecipitated compounds'are left in the completed emulsion. The amount ofwater contained in the emulsion is not critical as long as there isenough present to produce a stable water-reducible emulsion. Suitableamounts may vary from one part of water for every ten parts of rubbersolution to 10 parts of water for every part of rubber solution.

The advantages of the invention will be better understood from' aconsideration of the following experimental data which are given forthe' sake of illustration, but without intention'of limiting'theinvention thereto.

Example I cc. of a 50% solution of an oil (prepared by copolymerizing80% butadiene and 20% styrene in accordance with the disclosures ofcopending application Serial No. 176,771, filed July 29, 1950, in thename of Anthony H. Gleason, now U. S. Patent 2,762,851) are reacted with1% maleic anhydride in accordance with the disclosures of'U. S. Patent2,652,342issued'September 15,

1953, in the name of Anthony H; Gleason and mixed in a mechanicalagitator with 100 cc. of 1% sodium hydroxide solution. Approximately 150cc. of a jelly-like layer separated from the Water. One gram of thisjelly was dissolved in 200 cc. of n-hexane and poured into 150 cc. ofwater while agitating. The mixing was continued for 3 minutes whereupona stable emulsion with a viscosity about like that of water was formed.Further addition of up to 3 parts of water to 1 part of hydrocarboncaused the material to become increasingly viscons and finally a stablepaste. The emulsion showed no signs of breaking after standing for aday.

Example II One gram of the emulsifier jelly prepared in accordance withExample I was dispersed in 10 cc. of hexane. This was then dissolved in200 cc. of 50% NVM polymer oil prepared by copolymerizing 80% butadieneand 20% styrene with sodium in accordance with the teachings of SerialNo. 176,771. This solution was then added with agitation to 200 cc.water. The agitation was continued for three minutes whereupon a stableemulsion of low viscosity was formed. This emulsion showed no sign ofbreaking after a day. If desired the solvent may be removed from thelatex by evaporation or stripping with no adverse efiect upon theemulsion.

Example III 100 grams of a petroleum resin having a softening point ofabout 100 C. and made by Friedel-Crafts low temperature polymerizationof steam-cracked petroleum streams were reacted with 5 grams of maleicanhydride at 200 C. for 3 hours. Ten cubic centimeters of a solution ofthe resulting adduct in a hydrocarbon solvent was added to 200 cc. of a50 wt. percent solution of the original petroleum resin. The mixture waspoured slowly into 215 cc. of 0.35% caustic in a Waring Blendor andagitated for three minutes. At the end of this time a good emulsionformed which showed some evidence of creaming after standing overnightbut which was readily dispersed by mild shaking.

Example IV 100 grams of the petroleum resin of Example III were reactedat 200 C. for three hours with 0.2 gram of maleic anhydride. 96.5 gramsof this material were dissolved in 145 cc. of hexane to give a 50 wt.percent solution. Two hundred cubic centimeters of this solution wereslowly added to 200 cc. of 1% sodium hydroxide solution in a WaringBlendor and agitation continued for 3 minutes. An excellent emulsion wasformed which showed no signs of breaking after 1 day.

The latices obtained in accordance with this invention are suitable foruse in the preparation of foam rubber sponge extenders, paper size,paper shades and drapes, tire cord coating compositions, emulsionpaints, resilient concrete, laminant for paper, wood, canvas andplywood, binder for cork, wood, fiber, and leather buflings, industrialgloves and protective clothing, raincoating, rug backing and otherdipped goods and in adhesives.

The nature of the present invention having been thus fully set forth andspecific examples of the same given, what is claimed as new and usefuland desired to be secured by Letters Patent is: p

1. A process for preparing an emulsion of hydrocarbon polymer whichcomprises emulsifying a high molecular weight polymer with water in thepresence of the addition product of an unsaturated polymer selected fromthe group consisting of isobutylene and isoprene copolymers, isobutyleneand styrene copolymers, butadiene and styrene copolymers, butadiene andacrylonitrile copolymers, polybutadiene-and steam-cracked petroleumresins, and an anhydride selected from the group consisting of maleicanhydride, chloromaleic anhydride and citraconic anhydride neutralizedwith a compound selected from the group consisting of alkali metalhydroxides, alkali metal carbonates, ammonium hydroxide, ammoniumcarbonate and organic bases.

2. A process for preparing an emulsion of an unsaturated hydrocarbonpolymer which comprises reacting said unsaturated polymer selected fromthe group consisting of isobutylene and isoprene copolymers, isobutyleneand styrene copolymers, butadiene and styrene copolymers, butadiene andacrylonitrile copolymers, polybutadiene and steam-cracked petroleumresins with .01 to 5.0% of an anhydride selected from the groupconsisting of maleic anhydride, chloromaleic anhydride and citraconicanhydride whereby anhydride groups are introduced into a small portionof said polymer, neutralizing the said anhydride groups with a compoundselected from the group consisting of alkali metal hydroxides, alkalimetal carbonates, ammonium hydroxide, ammonium carbonate and organicbases whereby the salt of the anhydride-polymer adduct is formed, addingwater and emulsifying the said polymer in the presence of said salt asemulsifier.

3. A process for preparing an emulsion of an unsaturated hydrocarbonpolymer Which comprises reacting said unsaturated polymer selected fromthe group consisting of isobutylene and isoprene copolymers, isobutyleneand styrene copolymers, butadiene and styrene copolymers, butadiene andacrylonitrile copolymers, polybutadiene and steam-cracked petroleumresins with 0.1 to 0.5% of an anhydride selected from the groupconsisting of maleic anhydride, chloromaleic anhydride and citraconicanhydride, adding an aqueous solution of a compound selected from thegroup consisting of alkali metal hydroxides, alkali metal carbonates,ammonium hydroxide, ammonium carbonate and organic bases, and

agitating.

4. A process for preparing an emulsion of an unsaturated hydrocarbonpolymer which comprises reacting said unsaturated polymer selected fromthe group consisting of isobutylene and isoprene copolymers, isobutyleneand styrene copolymers, butadiene and styrene copolymers, butadiene andacrylonitrile copolymers, polybutadiene and steam-cracked petroleumresins with .01 to 5.0% of an anhydride selected from the groupconsisting of maleic anhydride, chloromaleic anhydride and citraconicanhydride whereby anhydride groups are introduced into a portion of saidpolymer, neutralizing the said anhydride groups with an alkali metalcompound, whereby the salt of the anhydride-polymer adduct is formed,adding water and emulsifying said polymer in the presence of said salt.

5. An emulsifying agent comprising the neutralization product of acompound selected from the group consisting of alkali metal hydroxides,alkali metal carbonates, ammonium hydroxide, ammonium carbonate andorganic bases, and the addition product of an unsaturated hydrocarbonpolymer selected from the group consisting of isobutylene and' isoprenecopolymers, isobutylene and styrene copolymers, butadiene and styrenecopolymers, butadiene and acrylonitrile copolymers, polybutadiene andsteam-cracked petroleum resins, and 0.01 to 5% of an anhydride selectedfrom the group consisting of maleic anhydride, chloromaleic anhydrideand citraconic anhydride.

6. Process according to claim 1 in which the second polymer is a liquidcopolymer of butadiene, and 20% styrene, the anhydride is maleicanhydride and the compound is sodium hydroxide.

7. Process according to claim 6 in which the first polymer is a liquidcopolymer of 80% butadiene and 20% styrene.

8. Process according to claim 1 in which the second polymer is asteam-cracked petroleum resin.

9. Process according to claim 8 in which the first polymer is asteam-cracked petroleum resin.

10. Process according to claim 3 in which the unsaturated polymer is aliquid copolymer of 80% butadiene and styrene.

11. Process according to claim 3 in which the unsaturated polymer is'asteam-cracked petroleum resin.

12. A process for preparing an emulsifying agent which comprises mixing20 to 80% of an unsaturated hydrocarbon polymer with 80 to 20% of asolvent consisting of an inert hydrocarbon boiling between 150 and 250C., adding 0.01 to 5 parts per 100 parts of polymer of an anhydrideselected from the group consisting of maleic anhydride, chlorornaleicanhydride and citraconic anhydride, heating the resulting mixture to to250 C. until an adduct forms and neutralizing theresulting adduct with acompound selected from the group consisting of alkali metal hydroxides,alkali metal carbonates, ammonium hydroxide, ammonium carbonate, andorganic bases.

13. Process according to claim 12 in which the unsaturated polymer is aliquid sodium copolymer of to parts of butadiene-1,3 and 15 to 25 partsof styrene.

14. Process according to claim 13 in which the anhydride is maleicanhydride.

15. Process according to claim 14 in which the adduct is neutralizedwith sodium hydroxide.

16. Process according to claim 12 in which the unsaturated polymer is asteam-cracked petroleum resin.

17. Process according to claim 16 in which the anhydride is maleicanhydride.

18. Process according to claim 17 in which the adduct is neutralizedwith sodium hydroxide.

19. An emulsifying agent comprising the sodium salt of the additionproduct of a sodium copolymer of 75 to 85 parts of butadiene-1,3 and 25to 15 parts of styrene with 0.1 to .5 part of maleic anhydride.

20. An emulsifying agent comprising the sodium salt of the additionproduct of a steam-cracked petroleum resin and maleic anhydride.

References Cited in the file of this patent UNITED STATES PATENTS1,976,679 Fikentscher et al Oct. 9, 1934 2,047,398 Voss et a1 July 14,1936 2,575,750 Davison Nov. 20, 1951 2,634,256 Sparks Apr. 7, 19532,652,342 Gleason Sept. 15, 1953 2,753,318 Maeder July 3, 1956

1. A PROCESS FOR PREPARING AN EMULSION OF HYDROCARBON POLYMER WHICHCOMPRISES EMULSIFYING A HIGH MOLECULAR WEIGHT POLYMER WITH WATER IN THEPRESENCE OF THE ADDITION PRODUCT OF AN UNSATURATED POLYMER SELECTED FROMTHE GROUP CONSISTING OF INSOBUTYLENE AND ISOPRENE COPOLYMERS,ISOBUTYLENE AND STYRENE COPOLYMERS, BUTA DIENE AND STYRENE COPOLYMERS,BUTADIENE AND ARCYLONITRILE COPOLYMERS, POLYBUTADIENE AND STEAM-CRACKEDPETROLEUM RESINS, AND AN ANHYDRIDE SELECTED FROM THE GROUP CONSISTING OFMALEIC ANHYDRIDE NEUTRALIZED WITH A COMPOUND CITRACONIC ANHYDRIDENEUTRALIZED WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALIMETAL HYDROXIDES, ALKALI METAL CARBONATES, AMMONIUM HYDROXIDE, AMMONIUMCARBONATE AND ORGANIC BASES.